Coating composition



.Patented May 4, 1937 UNITED sT-Arss con'rmc. comosmon Alfonso M.Alvarado, Wilmington, DeL, assignor to E. L du Pont de Nemonrs &CompamyWilon, Del., a corporation of Delaware 1 No Drawing. ApplicationNovember 28, 1933.

Serial No. 700,159

1 Claims. (Cl. 134-51) 7 This invention relates to coating.comp'ositiona. and more particularly to compositions containing, asphaltwhich are especially useful in the manufacture of coated fabrics,automobile top material.

5 and artificial leather products in general.

Coating compositions comprising asphalts and drying this, includingChina-wood oil, have been used for the top,coat in finishing rubbercoated fabrics. It has not, however, been possible in .the 10'compatibility of China-wood oil with asphalt because the heat treatmentof the oil which has previouslybeen used to overcome the tendency of thefilm to frost, decreases the'compatibility of the oil with the asphalt,this leads to a decrease in the properties of durability and longretention of luster which are most desired in automobile top materialand like products.

I f This invention has as an object the production 20 of improvedasphalt-containing coating compositions which dry toa smooth-glossyfilm. A further object of this invention is the production ofasphalt-raw China-wood oil coating compositions i which dry to 'a smoothglossy film. A still further 5 object of this invention is themanufacture of improved artificial leather products of the typeconsisting ofiabrics, and more particularly rubbercoated fabrics, havinga top coat or varnish comprised of asphalt and drying oil. I

30 I have discovered that the exceptional compatibility of rawChina-wood oil and asphalt may be utilizedfor the production of improvedcoated fabrics of the kind referred to above, and that'the initi lluster and luster retention qualities upon 5pm] nged outdoor exposure offinishes of this type are remarkably enhanced by i'neorporatio'n'oicertain compounds or agents into the asphalt-raw China-wood oil varnish,such as organic hydroxy compounds of low volatility, e. g., boilingabove about 200 C. and preferably above 250 C., and .which are solublein either hydrocarbon solvents, or alcohols, or esters. Aminocompoundsof similar boiling point, volatility and solubility characteristicsmayalso be used. The organic hydroxy 45 compounds include high boilingmonohydric alcohols, high boiling cyclic and alicyclic 'monohydricorpolyhydrlc alcohols, mononuclearand'polynuy 'clear monohydric an'c'ipolyhydric phenols which 50 may or may not contain additionalsubstituent groups,'hydroxy organic acids, etc. The amino compoundsinclude mononuclear amines such as toluidine, and polynuclear aminessuch as alphaand beta-naphthylamines, 5 In the preferred-method ofmaking my new prior practice to take advantage of the excellent varnish,I blend a solution of the asphalt with a solution of the raw China-woodoil containing one or more of the agents just mentioned. The agent maybe incorporated into the oil as a solution in alcohol or in an aromatichydrocarbon solvent .5 such as benzene, toluene, solvent naphtha, etc.,or it may be incorporated into the oil by heat treatment for asufiicient time to efiect complete solution of the agent in the oil, butinsuificient to bring about appreciable bodying of the oil. Thefollowing examples will serve to illustrate the invention: I

' Example 1 v V Parts Steam refined petroleum residue aspha1t 100.0 rRaw China-wood oil. 59.7 Hydroxydiphenyl (para) 0.3 Solvent naphthanuan, 160.0 Iron resinate solution in solvent naphtha I 345.0 Emmple2 I a Q 7 Parts Steam refined petroleum residue asphalt--- 100.0 RawChina-wood oil 157.6 Phenol A I 2.4 Solvent naphtha 260.0 Iron resinatesolution in solvent naphtha (2.4% Fe) Y 66.7

586.7 v Emmple'3 Parts- Steam refined petroleum residue asphalt 100.0 1Raw China-wood oil 117.0 Syringic acid a 2.4 Solvent naphtha 220.0 40Iron oleate solution insolvent naphtha (4% Fe) I 30.0

" a 4"1o.'o

Emmp e r Parts Steam refined petroleum residue asphalt 100.0 RawJapanese-wood oil 77.6 Diphenylguanidine a; 2.4 Solvent naphtha"; 180:0Iron linoleate solution in solvent naphtha Example 11 Example 5 PartsParts Gilsonite 14.00 Steam refined petroleum residue asphalt 100.0 RawChina w0od 011 37.62 Raw China-wood oil cr ol 0.38 Naphthylamine (alpha)1m resinate 72% 5.28 Solvent naphtha 180-0 china 51 9.00 Lead resinatesolution in solvent naphtha Bone m 3.00 Pb) Turpentine substitute 0-Manganese resinate solution in solvent naphtha (3.32% Mn) 1.2 100.00

' ExamplelZ t Par s 365.2 Gilsonite 8.56 Example 6 Raw China-wood oil14.67 Parts Bodied linseed oil 16.20 Blown petroleum residue asphalt 10Xy yl (ortho) g8; Raw China wod oil 157.6 Iron reslnate (7.2% Fe)Prussian blue (45.5% Fe) 0.52 Naphthol (alpha) 2.4

China clay 4.00 Solvent naphtha Carbon black f; in went i Turpentineubstitute 50.00 Manganese resinate solution in solvent 10000 naphtha(3.32% Mn) 2- Example 13 Parts 530.4 Gilsonite 3.2

Raw China-wood oil W Raw linseed oil 10.90 Parts Naphthol (beta) 0.21Blown petroleum residue asphalt 100.0 'Iron resinate (7.2% Fe) 4.30 Rawoiticica oil 99.5 Carbon black; 8.00 1-benzyl-2-naphthol1 Turpentinesubstitute 47.34 Solvent naphtha 200.0 Iron laurate solution in solventnaphtha 100.00

(4% Fe) 25.0 Example 14 Parts 4251 GilSOIlitB 7.54 Raw China-wood oil18.46 Emmple 3 China-wood oil acid 8.15 Parts Abietic acid. 0.57Gflsonite 1344 Iron resinate (7.2% Fe) 3.78 Raw China-wood oil 24.89China 11-00 pyrogauol (m3 Super-Spectra black 6.00 Lead-manganeseresinate drier (6.42% Pb, Solvent naphtha 4450 1.5% Mn) 0.64 00 Chinaclay 11.00 Carbon black. 5.50 All the asphalt-raw China-wood oilvarnishes Turpentine substitute 44.50 exemplified above have excellentdurability and luster retention upon prolonged exposure to the 100,00weather when used as baked finishes for rubber Emmple 9 coated fabrics.This excellent durability seems to be relatively independent of thegallon length I Parts of the varnishes, but I generally prefer to useGllsonite 10.81 high proportions of pigment in varnishes of long- RawChina-wood oil. 26.11 er gallon length than 20 gallons. Benzyl alcohol0.67 From 0.1 to 5% of the agent, based on the Iron oleate'(4% Fe) 3.35weight of the raw China-wood oil, may be used. China clay 11.00 Ingeneral, I prefer to use from 1 to 3% of the Carbon black 5.50 agentbased on the weight of the oil. The exact Turpentine substitute 42.56proportion oi. the agent to be used depends to a large extent both uponthe particular agent used 100.00 and upon the gallon lengthof thevarnish which it is. desired to prepare. If varnishes of rela- Example10 tively long gallon length are desiredfit is prefer Parts able to useas large a proportion of the agent Gilsonite 16.00 as practicable. Onthe other hand, if varnishes Raw China-wood oil. 33.97 of less than 15gallons in oil length are desired, Resoreinol 0.69 I prefer to use about2% of the agent on the Lead manganese resinate drier (6.42% 219- V 7weight of the oil. Varnishes of less than 20 gal- 1.52% Mn) 0.52 Ions inoil length are preferably prepared using Talc 4.00 petroleum residueasphalt, whereas varnishes of Carbon black 2.00 longer gallon lengththan 20 gallons are prefer- Turpentine substitute 42.82 ably preparedeither with gilsonite r t v loo 0 essed gilsonite having compatibilitycharacteristics similar to those of gilsonite. By gallon length inthevarnish trade is meant a gallon of oil to 100 pounds of gum. A gallon ofoil is generally considered to weigh 8,pounds. Accordingly a gallon oillength, as used herein, designates 8 pounds. of oil per 100 pounds ofasphalt. As pointed out above,ioompositions up to gallons in oil lengthare preferably prepared using petroleum residue asphalt and no pigment,whereas compositions of longer .gallon length than 20 gallons arepreferably prepared using. gilsonite,

or other natural asphalt having similar compatibility characteristics,and high proportions of pigment. In the pigmented varnishes, I prefer touse apigment combination comprising an inert pigment and a carbon black,as for example,

Super-Spectra black, microcosmic black, boneblack', etc. The inertpigment may be china clay, asbestine, Super-Floss, or any of the inertpigments ordinarily used, in paints and varnishes.

Carbon .black may be used alone, but in such cases the pigment contentshould be lowered to compensate for the oil absorption of the carbonblack. I prefer to use pigment contents varying from 12-40%, based onthe solids content of the varnishes. The ratio .of inert pigment tocarbon black may be varied in any desired proportion, 'but I prefer touse from one to two parts by weight of the inert'pigment to one of thecarbon black. 11 it is desired to pigment varnishes of lower gallonlength than 20 gallons, the per- 'centage of high oil absorptionpigment, e. g., carbon black, should be decreased and the percentage of'low oil absorption pigments, e. g.,

china clay, increased. For example, in a 10 gallon' varnish the carbonblack is one-half, or preferably one-third, of the total pigment, theremainder being china clay or other low oil absorption pigment. i

Addition of the agents described in this invention to asphalt-rawChina-wood oil varnishes not inhibit the drying qualitiesof thesevarnisheswhenthey are applied over rubber-coated fabrics and the systembaked at the vulcanizing temperature of therubben Moreover, addition as.I

resins containing some free phenol, etc.; rosin of these agents does notin any way decreasethe compatibility characteristics of the oil with theasphalt. Accordingly, using raw China-wood oil it is possible to preparevarnishes which have entirely satisfactory initial qualities in regard$0 luster, color, and smoothness of films up to gallons -in oil length,using petroleum residue asphalt, and even up to 50 gallonswhen-gilsonite or other natural asphalt having similar compatibilitycharacteristics as the asphalt Among the additional agents falling underthe,

general type previously described which'may be mentioned as being usefulin the practice of my invention are phenols such as vanlllic acid,nitro-- phenol, eugenol, guaiacol, kojic acid, and resorcinol;guanidines such as diphenyland triphenylguanidines; aromatic alcoholssuch as benzyl alcohol, xylyl alcohol; high boiling aliphatic alcohols,such as methylheptanolyor'ganic hydroxy acids" such as tartaric, mucicmalic, lactic, and citric acids: oil.- soluble phenol-formaldehyde estergum, congo ester and similar esterifled acidic gums: polyalkylamidessuchas dimethyl adipamide, etc.; aromatic amines such as methylaniline,etc. Combinations of raw China-wood ou with other oils such as linseedoil, soya bean oil, Menhaden oil, free fattyacids derived from drying,semi-drying or non-drying oils, oil modified polyhydricalcohol-polybasic acid resins may be used in these varnishes.

- gives even better results in respect to initial appearance anddurability, the varnishes are ap-- plied over an intermediate coat ofoil varnish. In the one coat system outlined above, it is usual to bakeat 240 F. to 270 F. for two to four hours to vulcanize the rubber anddry the varnish. In

the two coat system, the intermediate coat of oil varnish is usuallydried by baking at 240 F. to 270 F. for fifteen to thirty minutes, thefinal coat of asphalt varnish applied, and the system baked at 240 F. to270 F. for two to four hours to' 'vulcanize the rubber and dry the finalcoat of asphalt varnish. The particular temperature at Y which thesystem isbaked, in either the one coat or two coat systems, isdetermined by the composition of the rubber ,compoun'd. These varnisliesmay also be used as top dressings and in fender enamels.

The asphalt-raw China-wood 'oil varnishes made by thepractice of thisinvention are superior to prior art varnishes in their excellent initialappearance and their durability on prolonged exposure tothe weather. Thesuperior compatibility is shown by the fact that varnishes up to 25gallons in oil length can beprepared using steam refined petroleumresidue asphalt, and these varnishes dry to smooth glossy films whenthey are applied over rubber-coated fabrics. In the absence of agents ofthe kind described above,

asphalt-raw China-wood oil varnishes of longer gallon length than 7 /2gallons (60 pounds of oil per 100 pounds of asphalt) are notsatisfactory because of severe frosting upon drying. ingly, by using theprocedure outlined herein, I have shown that it is possible to use rawChinawood oil in varnishes of considerably longer gallon length than hasbeen hitherto possible. The

Accord practice of my invention makes it practicable to use rawChina-wood oil, and other oleostearin containing oils in asphaltvarnishes for use as finishes for rubber-coated fabrics and therebyobtains. finish which in addition to being free fromfrosting is, due tothe increased compatibility obtained with the raw China-wood oil overthat obtained with heat treated China-wood oil,

markedly improved in durability, initialluster and capability ofretaining the original high gloss upon long exposure to the weather.Twenty gallon steam refined petroleum residue asphalt-raw China-wood oilvarnishes containing the agents described herein have excellent initialappearance, whereas steam refined petroleum residue.

asphalt-bodied China-wood oil varnishes of simiagents described abovelar gallon length prepared by the prior art practice of heating the oilto prevent frosting have very poor initial'appearance when they areprepared in the absence of driers, Moreover, 20 gallon steam refinedpetroleum residue asphaltraw" China-wood oil varnishes containing thel:lry satisfactorily upon baking for two and oneuarter totwo and onehalfhours (when applied over rubber-coated fabrics), even in the absence ofdriers, whereas varnishes of similar gallon length but containing afterlong exposure to the weather.

As many apparently widely difi'erent embodiments of this invention maybe made without departing from the spirit and scope thereof, it is ntobe understood that I do not limit myself to the specific embodimentsthereof except as defined in the following claims:

I claim: a

1. A coating composition, the films of which 5 are substantially freefrom frosting and wrinkling upon drying, said composition comprising ananti-wrinkling agent and a homogeneous mixture of raw China-wood oil andasphalt containing between 60 and 400 pounds of raw China-wood oil foreach hundred pounds of asphalt, said agent being selected from the classconsisting of organic hydroxy compounds and amines, and having a boilingpoint above 200 C.

2. The composition of claim 1 in which the anti-wrinkling agent ispara-hydroxydiphenyl and is present in amount from 0.1 to 5% of theweight of China-wood oil in the composition.

3. The composition of claim 1 in which the anti-wrinkling agent isbeta-naphthol and is present in amount from 0.1 to 5% of the weight ofChina-wood oil in the composition.

4. The composition of claim 1 in which the anti-wrinkling agent isalpha-naphthylamine and is present in amount from 0.1 to 5% of theweight of China-wood oil in the composition.

ALFONSO M. ALVARADO.

